JP2017119267A - Catalyst for manufacturing aromatic compound and method for manufacturing aromatic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for manufacturing an aromatic compound excellent in productivity, stability, swing operability, and long life, and a manufacturing method of the aromatic compound.SOLUTION: There is provided a catalyst for manufacturing an aromatic compound, containing MFI type zeolite satisfying properties represented by following (i) to (iii). These properties include: (i) mesopores having mesopore distribution curve with a peak, half value width (hw) of the peak of hw≤20 nm, maximum value (μ) of the peak of 10 nm≤μ≤20 nm, and mesopore volume (pv) of the mesopore corresponding to 0.05 ml/g≤pv; (ii) no peak in a range of 0.1 to 3 degree in a powder X ray diffraction measurement with diffraction angle of 2θ; and (iii) average particle diameter (PD) being PD≤100 nm.SELECTED DRAWING: None

Description

  The present invention relates to an aromatic compound production catalyst containing a specific MFI type zeolite and a method for producing an aromatic compound using the same, and in particular, production containing an MFI type zeolite having relatively uniform mesopore groups. The present invention relates to an aromatic compound production catalyst having excellent properties, stability, swing driving performance, and long life, and an aromatic compound production method using the same.

  MFI-type zeolite is used as a highly selective catalyst utilizing uniform pores derived from the zeolite structure. Examples of using MFI type zeolite as a catalyst include disproportionation of toluene (for example, see Patent Document 1), isomerization of xylene (for example, see Patent Document 2), and the like.

  These reactions mainly utilize the micropore characteristics of MFI-type zeolite. The MFI-type zeolite micropore has an inlet diameter of about 0.5 nm and is considered to be an effective reaction field for molecules having a molecular diameter close to the pore diameter.

  Furthermore, research on MFI type zeolite having pores larger than micropores (less than 2 nm), that is, mesopores (pore diameter 2 to 50 nm) has been conducted (for example, see Non-Patent Document 1).

  As a promising material for industrial use, a novel MFI-type zeolite having uniform mesopores of 10 nm or more and a production method thereof (see, for example, Patent Document 3) have been proposed. As an example used as a catalyst, fluid catalytic cracking (FCC) of vacuum gas oil using ultrastable Y-type zeolite (USY) (for example, see Patent Documents 4 and 5) has been proposed. Since the process includes advancing a catalytic cracking reaction using heavy oil as a raw material, a catalyst having pores capable of diffusing large size molecules equivalent to heavy oil is desired. Cases using mesoporous zeolites as catalysts have been limited to those using relatively large spaces inside mesopores as reaction fields and relatively large molecules such as heavy oil as raw materials. . For this reason, there are few reports that specific results were obtained by using zeolite having mesopores as a catalyst, particularly in reactions using relatively small molecules having 10 or less carbon atoms as raw materials.

  In many cases, benzene, toluene, and xylene (hereinafter collectively referred to as aromatic compounds) are obtained by cracking raw oil (for example, naphtha) obtained by petroleum refining in a thermal decomposition reactor. It is obtained by separating and purifying an aromatic compound from the obtained thermal decomposition product by distillation or extraction. In the production of aromatic compounds by these production methods, aliphatic and alicyclic hydrocarbons are included as thermal decomposition products other than aromatic compounds. Therefore, since the aliphatic and alicyclic hydrocarbons are produced simultaneously with the production of the aromatic compound, the production amount of the aromatic compound is adjusted according to the production amount of the aliphatic and alicyclic hydrocarbons. Naturally, production was limited. Moreover, an aromatic compound can be produced by bringing an aliphatic or alicyclic hydrocarbon raw material into contact with a catalyst mainly containing a medium pore size zeolite at a temperature of about 400 ° C. to about 800 ° C. ( For example, non-patent documents 2 to 5). The production method has an advantage that the aromatic compound can be produced from an excess hydrocarbon raw material, as compared with the production method of the aromatic compound by pyrolysis, which has a low added value. In addition, development of catalysts used for the production of these aromatic compounds has also been carried out. For example, Patent Document 6 provides a zinc-supported intermediate pore size zeolite catalyst in which the amount of scattered zinc is suppressed as a catalyst for producing an aromatic compound using a hydrocarbon containing paraffin, olefin, and naphthene as a raw material. Alternatively, in Patent Document 7, platinum and a halogen component are simultaneously supported on L-type zeolite as a catalyst used in the production of an aromatic compound using paraffin, olefin, acetylene hydrocarbon, cyclic paraffin and cyclic olefin as raw materials. A catalyst is provided. Or in patent document 8, the magnitude | size of a structure is 0.1-100 mm, crystalline porous aluminosilicate exists in a structure surface layer part, and an inorganic support body exists in an internal layer except a structure surface layer part. There is provided a catalyst for aromatization reaction, characterized in that zinc and / or gallium are supported on a structure in which is present. In addition, Patent Documents 9 to 10 provide an aromatic compound production catalyst using a hydrocarbon as a raw material.

  In the aromatic compound production method using these catalytic reactions, from the viewpoint of production cost, the catalyst life (the time from when the catalyst is activated until the catalyst is deactivated after the reaction is started) becomes a problem. Therefore, a method for selectively producing an aromatic compound from a hydrocarbon raw material having a relatively small molecule (particularly having 10 or less carbon atoms) stably over a long period of time is very significant.

Japanese Patent No. 40114279 Japanese Patent No. 2598127 JP 2013-227203 A Japanese Patent No. 5339845 Japanese Patent No. 4773420 JP 1998-33987 Gazette Japanese Patent No. 3264447 Japanese Patent No. 5447468 Japanese Patent No. 3966429 Japanese Patent No. 5564769

Microporous and Mesoporous Materials 137, 92 (2011) Industrial & Engineering Chemistry Research Vol. 31, 995 (1992) Industrial & Engineering Chemistry Research Volume 26, 647 (1987) Applied Catalysis Volume 78, 15 (1991) Microporous and Mesoporous Materials 47, 253 (2001)

  An object of the present invention is to provide a novel fragrance capable of selectively producing an aromatic compound stably from a hydrocarbon raw material having a relatively small molecule (particularly having 10 or less carbon atoms) over a long period of time. An aromatic compound production catalyst and a method for producing an aromatic compound using the same are provided.

  As a result of intensive studies to solve the above problems, the present inventor has produced an aromatic compound selectively and stably over a long period of time by using an aromatic compound production catalyst containing a specific MFI type zeolite. As a result, the present inventors have found that the catalyst can be made, and have completed the present invention.

That is, the present invention includes an aromatic compound production catalyst comprising an MFI-type zeolite that satisfies the following properties (i) to (iii), and a group consisting of olefins having 2 to 6 carbon atoms: It is related with the manufacturing method of the aromatic compound characterized by contacting the lower olefin containing at least 1 among these, and making it an aromatic compound.
(I) The mesopore distribution curve has a peak, the half width (hw) of the peak is hw ≦ 20 nm, and the central value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, which corresponds to the peak The mesopore volume (pv) of the mesopores is 0.05 ml / g ≦ pv.
(Ii) No powder has a peak in the range of 0.1 to 3 degrees in powder X-ray diffraction measurement with a diffraction angle of 2θ.
(Iii) The average particle size (PD) is PD ≦ 100 nm.

  The present invention is described in detail below.

  The aromatic compound production catalyst of the present invention comprises a specific MFI-type zeolite. By containing a specific MFI-type zeolite, the aromatic compound can be selectively and stably stable over a long period of time. It becomes a catalyst that can be produced in a simple manner.

  The MFI type zeolite constituting the aromatic compound production catalyst of the present invention satisfies the characteristics shown in the above (i) to (iii), and the MFI type zeolite has a structure code MFI defined by the International Zeolite Society. It shows the aluminosilicate compound which belongs to. The mesopores referred to in the present invention are mesopores defined by IUPAC, and indicate pores having a pore diameter in the range of 2 to 50 nm. The mesopores can be measured by a general nitrogen adsorption method at a liquid nitrogen temperature. Further, by analyzing the measurement result obtained by the nitrogen adsorption method, the value of the pore volume of the mesopores can be obtained. For the analysis, for example, the following method can be used.

  Specific examples include a method of analyzing the desorption process by the Barret-Joyner-Halenda method (Journal of the American Chemical Society, 1951, pages 373-380). For example, the pore diameter is 2 nm to 50 nm. By accumulating the nitrogen gas desorption amount in a range corresponding to the above, the value of the total pore volume of the pores belonging to the mesopores can be obtained.

  First, after obtaining a cumulative curve in which the vertical axis represents nitrogen desorption amount per unit mass V / m (mL / g) and the horizontal axis represents mesopore diameter D (nm), the vertical axis represents mesopores. Of the desorption amount of nitrogen gas from the mesopore diameter value (d (V / m) / d (D)), the increase in the nitrogen desorption amount per unit mass in the mesopore diameter A peak can be obtained.

  The aromatic compound production catalyst of the present invention comprises an MFI type zeolite having a mesopore group having a substantially uniform pore diameter. In the present invention, the mesopores having a substantially uniform pore diameter are included. Groups may be referred to as uniform mesopores. Specifically, the uniform mesopore is a standard deviation from the center value (μ) of the Gaussian function that approximates the maximum peak of the mesopores in the pore distribution curve with a Gaussian function. Is a mesopore having a pore diameter in the range (μ ± 2σ) of twice (2σ). The pore volume of uniform mesopores can be determined by integrating the nitrogen gas desorption amount in the range of μ ± 2σ.

  The aromatic compound production catalyst of the present invention has (i) a mesopore distribution curve having a peak among MFI-type zeolites having a substantially uniform mesopore group, and the half width (hw) of the peak. ) Is hw ≦ 20 nm, the center value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, and the mesopore volume (pv) of the mesopores corresponding to the peak is pv ≧ 0.05 ml / g. It comprises MFI-type zeolite having a more uniform mesopore group.

  The aromatic compound production catalyst of the present invention has a peak in the pore distribution curve of mesopores, and the peak is an almost uniform meso with small variation in pore diameter of MFI-type zeolite having hw ≦ 20 nm or less. By including the MFI-type zeolite having the pore group, the reaction selectivity becomes excellent, and the effect becomes more markedly favorable by hw ≦ 15 nm. And although it does not set in particular as a minimum of hw, since it becomes what is more excellent in reaction selectivity, it is preferable that it is 1 nm or more. In addition, when hw> 20 nm, the reaction selectivity is poor. In addition, by including an MFI type zeolite having a center value (μ) of approximating the Gaussian function of the peak of 10 nm ≦ μ ≦ 20 nm, it becomes possible to selectively react even with larger size molecules. It becomes an aromatic compound production catalyst. Furthermore, when pv ≧ 0.05 ml / g, the catalyst becomes a long-life catalyst, and preferably 0.05 ml / g ≦ pv ≦ 0.70 ml / g, particularly 0.10 ml / g ≦ It is preferable that pv ≦ 0.7 ml / g, and further preferably 0.20 ml / g ≦ pv ≦ 0.5 ml / g. Here, when pv <0.05 ml / g, the pores are likely to be clogged due to accumulation of coke or the like by-produced during the reaction, resulting in poor catalyst life.

  Moreover, since the MFI type zeolite contained in the aromatic compound production catalyst of the present invention is a catalyst that enables a particularly selective reaction, the proportion of pv in the total pore volume shown in (i) above ( pvr) is preferably 30% ≦ pvr ≦ 100%, more preferably 40% ≦ pvr ≦ 100%.

  The MFI type zeolite contained in the aromatic compound production catalyst of the present invention does not have a peak in the range of 0.1 to 3 degrees in (ii) powder X-ray diffraction measurement with a diffraction angle of 2θ. This indicates that there is no regularity in the arrangement between mesopores and that there is no wall separating mesopores, and mass transfer between mesopores is easy when a catalyst is used. Therefore, it becomes an aromatic compound production catalyst having excellent reaction efficiency.

The MFI-type zeolite contained in the aromatic compound production catalyst of the present invention is (iii) PD ≦ 100 nm, and since it becomes an aromatic compound production catalyst particularly excellent in heat resistance, 3 nm ≦ PD. Preferably, 5 nm ≦ PD is more preferable. Here, in the case of a zeolite of PD> 100 nm, almost uniform mesopore groups are not formed, and selectivity is achieved. In addition, PD can be calculated | required, for example using the following formula | equation (1) from an external surface area.
PD = 6 / S (1 / 2.29 × 10 ⁶ + 0.18 × 10 ⁻⁶ ) (1)
(Here, S represents the outer surface area (m ² / g).)
Further, the outer surface area (S (m ² / g)) in the formula (1) can be obtained from the t-plot method using a general nitrogen adsorption method at a liquid nitrogen temperature. For example, when t is the thickness of the adsorption amount, a measurement method in the range of 0.6 to 1 nm for t is linearly approximated, and the outer surface area is obtained from the slope of the obtained regression line.

  In addition, as another method for measuring the particle diameter of MFI-type zeolite, for example, 10 or more arbitrary particles are selected from a photograph of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the surface area average diameter is selected. Can be mentioned.

The MFI type zeolite contained in the aromatic compound production catalyst of the present invention is not limited in its SiO ₂ / Al ₂ O ₃ (molar ratio), and among them, a catalyst excellent in heat resistance, reaction selectivity, and productivity Therefore, the SiO ₂ / Al ₂ O ₃ (molar ratio) is preferably 20 or more and 200 or less.

  Since the MFI type zeolite contained in the aromatic compound production catalyst of the present invention is a catalyst excellent in reaction selectivity and productivity, it does not contain a structure directing agent such as tetrapropylammonium salt in the pores. Preferably there is.

  The form of using the MFI-type zeolite as the aromatic compound production catalyst of the present invention is not limited. For example, the synthesized MFI-type zeolite powder is used as a catalyst as it is, or a specific shape is formed by compression molding. It can be used in any form, such as being used as a product, mixed with a binder or the like, molded and used as a specific shape.

  The aromatic compound production catalyst of the present invention is an aromatic compound production catalyst having excellent efficiency such as reaction selectivity and productivity by including the MFI-type zeolite. An aromatic compound can be efficiently produced by contacting with a hydrocarbon. In this case, the hydrocarbon having 2 to 6 carbon atoms may be any hydrocarbon as long as it belongs to the category, for example, saturated hydrocarbon, unsaturated hydrocarbon, alicyclic hydrocarbon, a mixture thereof, and the like. More specifically, ethane, ethylene, propane, propylene, cyclopropane, n-butane, isobutane, 1-butene, 2-butene, isobutene, butadiene, cyclobutene, cyclobutane, n-pentane, 1- Pentane, 2-pentane, 1-pentene, 2-pentene, 3-pentene, n-hexane, 1-hexane, 2-hexane, 1-hexene, 2-hexene, 3-hexene, hexadiene, cyclohexane and mixtures thereof Can be mentioned.

  And the aromatic compound manufacturing catalyst of this invention becomes an aromatic compound manufacturing catalyst excellent in efficiency, such as reaction selectivity and productivity, by including this MFI type zeolite, An aromatic compound can be efficiently produced by contacting with at least one lower olefin of the group consisting of 6 olefins. Examples of the olefin at that time include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 1-hexene, 2-hexene, 3-hexene, and mixtures thereof. Can be mentioned.

  Further, by contacting a hydrocarbon mixture having 4 carbon atoms with a catalyst comprising the MFI-type zeolite, a method for producing an aromatic compound having excellent efficiency such as reaction selectivity and productivity is obtained. Examples of the hydrocarbon mixture of number 4 include those called as C4 fractions among the cracked fractions of petroleum such as naphtha. More specifically, n-butane, isobutane, 1 Examples thereof include a mixture comprising -butene, 2-butene, isobutene, butadiene, cyclobutene, cyclobutane and the like.

  By contacting a hydrocarbon mixture having 6 carbon atoms with a catalyst comprising the MFI-type zeolite, a method for producing an aromatic compound having excellent efficiency such as reaction selectivity and productivity is obtained. As the hydrocarbon mixture, there can be mentioned, for example, what is referred to as a C6 fraction among the cracked fractions of petroleum such as naphtha. Examples thereof include a mixture of n-hexane, 1-hexene, 2-hexene, hexadiene, cyclohexane and the like.

  Furthermore, the aromatic compound production catalyst of the present invention is a conversion catalyst having excellent efficiency such as reaction selectivity and productivity by including the MFI-type zeolite. An aromatic compound can be efficiently produced by contacting with an aliphatic hydrocarbon or an alicyclic hydrocarbon. Examples of the saturated aliphatic hydrocarbon or alicyclic hydrocarbon at that time include ethane, propane, butane, isobutane, pentane, hexane, cyclopropane, cyclobutane, cyclohexane, and mixtures thereof.

In the reaction that is an embodiment at that time, the reaction temperature is not particularly limited as long as an aromatic compound can be produced. Among them, the production of olefin or alkane is suppressed, and heat resistance more than necessary is required. The range of 400 to 800 ° C. is desirable because an efficient reaction of an aromatic compound that does not require a reaction apparatus. Moreover, there is no restriction | limiting also in reaction pressure, For example, it can drive | operate in the pressure range of about 0.05 MPa-5 MPa. Then, the supply of olefin and the reaction raw material to the aromatic compound production catalyst of the present invention is not particularly limited as the ratio of the volume of raw material gas to catalyst volume, for example, the space of about 1h ^-1 ~50000h ^-1 Speed can be mentioned. When supplying olefin as a raw material gas, the olefin is diluted with a single gas or a mixed gas selected from an inert gas such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide. It can also be used as a thing.

  There is no restriction | limiting as the reaction format, For example, not only a fixed bed, a transport bed, a fluidized bed, a moving bed, a multitubular reactor but a continuous flow type, an intermittent flow type, a swing type reactor, etc. can be used. And since it becomes an especially efficient manufacturing method of an aromatic compound, it is preferable that it is the reaction format by a swing type reactor. The aromatic compound production catalyst of the present invention is preferably a catalyst for swing operation because of excellent production efficiency of the aromatic compound and long catalyst life and regeneration resistance.

  In addition, the aromatic compound to be produced is not particularly limited as long as it belongs to the category called aromatic compound, for example, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, propylbenzene, butylbenzene, naphthalene, Examples thereof include methylnaphthalene, and benzene, toluene, and xylene are particularly preferable.

  The present invention relates to an aromatic compound production catalyst containing a specific MFI-type zeolite, and in particular, when producing an aromatic compound from an olefin, a saturated aliphatic hydrocarbon, and an alicyclic hydrocarbon, a specifically long catalyst The present invention provides an aromatic compound production catalyst suitable for swing operation and a method for producing an aromatic compound using the same, and is very useful industrially.

Hereinafter, the present invention will be specifically described by way of examples.
The MFI type zeolite and aromatic compound production catalyst used in the examples were measured and defined by the following methods.

-Measurement of pore distribution, pore diameter, and outer surface area-
The pore distribution and pore diameter of the zeolite were measured by nitrogen adsorption measurement.

  Nitrogen adsorption measurement at that time was performed using a nitrogen adsorption device ((trade name) OMISORP 360CX, manufactured by Beckman Coulter) under both conditions of 30 torr / step. The outer surface area was obtained by linearly approximating the range of the adsorption layer thickness (t = 0.6 to 1.0 nm) by the t-plot method.

  Then, the desorption process of nitrogen adsorption measurement was analyzed by the Barret-Joyner-Halenda method (Journal of the American Chemical Society, 1951, pages 373-380), the horizontal axis is the pore diameter constant, and the vertical axis is nitrogen gas. A pore distribution curve of mesopores, which is a differential value of the desorption amount of, was obtained. The total pore volume of the mesopores was determined by integrating nitrogen gas desorption amounts in the range of 2 nm to 50 nm.

  And, the peak of the differential value (d (V / m) / d (D)) of the mesopore diameter value of the nitrogen gas desorption amount from the mesopores is analyzed by intensity approximation of Gaussian function. A mesopore having a diameter within the range (= μ ± 2σ) of the standard value (μ) of the Gaussian function and twice the standard deviation (2σ) was defined as a uniform mesopore. The pore volume of the uniform mesopores was determined by integrating the nitrogen gas desorption amount in the range of ± 2σ with the center value (μ) as a reference.

~ Measurement of average particle diameter ~
The average particle diameter was calculated from the outer surface area using the above formula (1). In formula (1), S is an external surface area (m ² / g), and PD is an average particle diameter (m). The outer surface area (S (m ² / g)) in the formula (1) was determined from the t-plot method by the nitrogen adsorption method at the liquid nitrogen temperature.

-Measurement of SiO ₂ / Al ₂ O ₃ molar ratio-
The SiO ₂ / Al ₂ O ₃ molar ratio of zeolite is such that MFI type zeolite is dissolved in a mixed aqueous solution of hydrofluoric acid and nitric acid, and this is inductively coupled plasma by a general ICP apparatus ((trade name) OPTIMA3300DV, manufactured by PerkinElmer). It measured and calculated | required by the emission spectral analysis (ICP-AES).

-Measurement of agglomerated diameter-
As aggregate diameter was measured volume average diameter of the aggregate particle diameter (D ₅₀₎ by a dynamic scattering method. (Trade name) Microtrac HRA (Model 9320-x100) (manufactured by Nikkiso) was used for the measurement. In the measurement, the particle refractive index was 1.66, the setting of the particles was transparent non-spherical particles, and the liquid refractive index of the solvent was 1.33.

~ Measurement of powder X-ray diffraction ~
Using an X-ray diffractometer (Spectris Co., Ltd., (trade name) X'pert PRO MPD), a tube voltage of 45 kV and a tube current of 40 mA were used in the atmosphere using CuKα1. The range of 0.04-5 degrees was analyzed at 0.08 degrees / step, 200 seconds / step. In addition, the background corrected by the absorptance of the direct beam is removed.

  The presence or absence of a peak can be confirmed visually, or a peak search program may be used. A general program can be used as the peak search program. For example, when the horizontal axis is 2θ (degrees) and the vertical axis is intensity (au), the measurement results are smoothed with the SAVITSKY & GOLAI equation and the sliding polynomial filter, and then subjected to second order differentiation, three or more points are continuous. If there is a negative value, it was judged that a peak was present.

-Aromatic compound production apparatus and production method thereof-
The aromatic compound production catalysts obtained in the examples were produced by the following method and evaluated.

  A swing type reactor in which two fixed bed gas phase flow reactors using stainless steel reaction tubes (inner diameter 16 mm, length 600 mm) were connected in parallel was used. After filling the middle stage of each of the two stainless steel reaction tubes with an aromatic compound production catalyst and performing pre-heating treatment under dry air flow, the two reactors are switched at predetermined intervals. The operation was performed and the raw material gas was fed alternately. While the raw material gas was supplied and reacted in one reactor (reaction side), air gas was circulated in the other reactor (regeneration side) to regenerate the aromatic compound production catalyst by coke combustion. The apparatus conditions and operating conditions of the swing reactor are not limited to those described in this example, and can be selected as appropriate. And heating used the ceramic tube furnace, and controlled the temperature of the catalyst layer. The reaction outlet gas and the reaction liquid were collected, and the gas component and the liquid component were individually analyzed using a gas chromatograph. The gas component was analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-1700) equipped with a TCD detector. As the filler, PorapakQ (trade name) manufactured by Waters or MS-5A (trade name) manufactured by GL Science was used. The liquid component was analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-2015) equipped with an FID detector. A capillary column (manufactured by GL Sciences, (trade name) TC-1) was used as the separation column.

  The reaction conditions were set as follows.

(Aromatic compound production conditions)
Catalyst temperature: 600 ° C.
Flowing gas: mixed gas of raw material gas 50 mol% + nitrogen 50 mol%, 100 ml / min.
Ratio of raw material gas volume to catalyst volume: 1000 / hour.
Catalyst weight: 1.5 g.
Catalyst shape: MFI-type zeolite powder was molded at 400 kgf / cm ² for 1 minute and then pulverized to give a pellet shape of about 1 mm.
Reaction pressure: 0.1 MPa.

(Catalyst regeneration conditions and air purge conditions during swing operation)
Catalyst temperature: 600 ° C.
Circulating gas: 50 ml / min of air.
Ratio of air gas volume to catalyst volume: 1000 / hour.
Pressure: 0.1 MPa.

(Nitrogen purge condition)
Catalyst temperature: 600 ° C.
Circulating gas: nitrogen 50 ml / min.
Ratio of nitrogen gas volume to catalyst volume: 1000 / hour.
Pressure: 0.1 MPa.

  The MFI-type zeolite was produced with reference to JP 2013-227203 A.

Example 1
Amorphous aluminosilicate gel was added and suspended in an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The amount of seed crystals added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. By-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized with stirring at 115 ° C. for 4 days to obtain a slurry mixture. The slurry-like mixed liquid after crystallization was subjected to solid-liquid separation with a centrifugal settling machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

  10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI zeolite. Thereafter, the ammonium type MFI zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 27 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an agglomerated diameter of 46 μm. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.39 ml / g. Further, the mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. Moreover, the pore volume of uniform mesopores was 0.31 ml / g, and the ratio of the pore volume of uniform mesopores to the total pore volume of mesopores was 78%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI type zeolite was used as an aromatic compound production catalyst, ethylene was used as a raw material, and an aromatic compound was produced under the conditions described above. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The source gas was passed through the reaction tube heated at 600 ° C. for 140 minutes, and then the source gas feed was immediately switched in the direction of the reaction tube on the regeneration side.

(Playback side)
At the same time as the feed gas feed of the reaction side reaction tube is started, a nitrogen purge (1) is started on the regeneration side reaction tube heated at 600 ° C. Replaced. Next, the supply gas was immediately switched from nitrogen to air, and an air purge was performed for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, the aromatic compound production catalyst was regenerated by circulating air for 60 minutes. Subsequently, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purge (3) was performed for 30 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, the nitrogen gas feed line was immediately switched in the direction of the reaction tube on the reaction side, and at the same time, the feed of the raw material gas was started in the reaction tube on the regeneration side. Thereafter, a series of processes similar to those described above were repeated to obtain a product feed continuously. The reactions described in the following examples and comparative examples were also operated in the same procedure, and only the raw material gas circulation time, the regeneration treatment time, and the nitrogen purge (3) time were changed. Table 2 shows the gas circulation time in each step.

  Table 3 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 1395 minutes.

Example 2
The MFI-type zeolite obtained in Example 1 was used as an aromatic compound production catalyst, propylene was used as a raw material, and a conversion reaction into an aromatic compound was performed under the conditions described above.

  Table 2 shows the gas circulation time in each step. Table 4 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to stably obtain the product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 2295 minutes.

Example 3
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added as a seed crystal to the aqueous solution to form a raw material composition, and ethanol produced as a by-product was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI type zeolite is 0.42 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopore The half width was 15 nm and μ = 17 nm. Moreover, the pore volume of the uniform mesopores was 0.39 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 92%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI type zeolite was used as an aromatic compound production catalyst, ethylene was used as a raw material, and a conversion reaction to an aromatic compound was performed under the above-described conditions.

  Table 2 shows the gas circulation time in each step.

  Table 5 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 1395 minutes.

Example 4
Using the MFI zeolite obtained in Example 3 as an aromatic compound production catalyst, a conversion reaction to an aromatic compound using propylene as a raw material was performed. The reaction was performed under the conditions described above.

  Table 2 shows the gas circulation time in each step. Table 6 shows the raw material gas distribution time, the conversion rate, and the yield of each product. It was possible to obtain a product feed continuously up to a raw material gas circulation time of 2295 minutes without any significant decrease in conversion, benzene yield, toluene yield, or xylene yield.

Comparative Example 1
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H ₂ O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was 180 ° C., to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of uniform mesopores in the pore distribution curve is 0.3 nm and μ = 4 nm. there were. Moreover, the pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, ethylene was used as a raw material, and the conversion reaction was performed under the above-described conditions.

  Table 2 shows the gas circulation time in each step.

  Table 7 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 1395 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 2
The conversion reaction was performed under the above-described conditions using the MFI zeolite obtained in Comparative Example 1 as a catalyst and ethylene as a raw material.

  Table 2 shows the gas circulation time in each step.

  Table 8 shows the raw material gas circulation time, the conversion rate, and the yield of each product. With an ethylene flow time of 535 minutes, the conversion rate was 51%, the benzene yield was 8 wt%, the toluene yield was 9 wt%, and the xylene yield was 2 wt%, and the productivity was poor.

Comparative Example 3
The conversion reaction was performed under the above-described conditions using the MFI zeolite obtained in Comparative Example 1 as a catalyst and propylene as a raw material.

  Table 2 shows the gas circulation time in each step.

  Table 9 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas distribution time of 2295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say that stable production.

Comparative Example 4
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half-width of the peak of uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. . Further, the pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

  The obtained MFI type zeolite was used as a catalyst, ethylene was used as a raw material, and a conversion reaction was carried out under the conditions described above.

  Table 2 shows the gas circulation time in each step.

  Table 10 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 1395 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say that stable production.

Comparative Example 5
The conversion reaction was performed under the above-described conditions using the MFI-type zeolite obtained in Comparative Example 4 as a catalyst and ethylene as a raw material.

  Table 2 shows the gas circulation time in each step.

  Table 11 shows the raw material gas flow time, the conversion rate, and the yield of each product. With an ethylene circulation time of 895 minutes, the conversion rate was 52%, the benzene yield was 10 wt%, the toluene yield was 8 wt%, and the xylene yield was 2 wt%, resulting in poor productivity.

Comparative Example 6
The conversion reaction was performed under the above-described conditions using the MFI-type zeolite obtained in Comparative Example 4 as a catalyst and propylene as a raw material.

  Table 2 shows the gas circulation time in each step.

  Table 12 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas distribution time of 2295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say that stable production.

Example 5
Amorphous aluminosilicate gel was added and suspended in an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The amount of seed crystals added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. By-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized with stirring at 115 ° C. for 4 days to obtain a slurry mixture. The slurry-like mixed liquid after crystallization was subjected to solid-liquid separation with a centrifugal settling machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

  10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI zeolite. Thereafter, the ammonium type MFI zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an agglomerated diameter of 46 μm. The total pore volume of mesopores present in the obtained MFI type zeolite was 0.40 ml / g. Further, the mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. Moreover, the pore volume of uniform mesopores was 0.32 ml / g, and the ratio of the pore volume of uniform mesopores to the total pore volume of mesopores was 80%. Table 13 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI type zeolite was used as an aromatic compound production catalyst, n-butane was used as a raw material, and an aromatic compound was produced under the above-described conditions. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The source gas was circulated through the reaction tube heated at 600 ° C. for 1000 minutes, and then the source gas feed was immediately switched in the direction of the reaction tube on the regeneration side.

(Playback side)
At the same time as the feed gas feed of the reaction side reaction tube is started, a nitrogen purge (1) is started on the regeneration side reaction tube heated at 600 ° C. Replaced. Next, the supply gas was immediately switched from nitrogen to air, and an air purge was performed for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, the aromatic compound production catalyst was regenerated by circulating air for 60 minutes. Subsequently, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purge (3) was performed for 890 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, the nitrogen gas feed line was immediately switched in the direction of the reaction tube on the reaction side, and at the same time, the feed of the raw material gas was started in the reaction tube on the regeneration side. Thereafter, a series of processes similar to those described above were repeated to obtain a product feed continuously. The reactions described in the following examples and comparative examples were also operated in the same procedure, and only the raw material gas circulation time, the regeneration treatment time, and the nitrogen purge (3) time were changed. Table 14 shows the gas circulation time in each step.

  Table 15 shows the raw material gas circulation time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significant reduction in the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 9995 minutes.

Example 6
Using the MFI zeolite obtained in Example 5 as an aromatic compound production catalyst, isobutane was used as a raw material, and a conversion reaction to an aromatic compound was performed under the conditions described above.

  Table 14 shows the gas circulation time in each step. Table 16 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 9795 minutes.

Example 7
The MFI-type zeolite obtained in Example 5 was used as an aromatic compound production catalyst, and n-hexane was used as a raw material, and a conversion reaction to an aromatic compound was performed under the above-described conditions.

  Table 14 shows the gas circulation time in each step. Table 17 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 10495 minutes.

Example 8
The MFI-type zeolite obtained in Example 5 was used as an aromatic compound production catalyst, methylcyclopentane was used as a raw material, and a conversion reaction to an aromatic compound was performed under the conditions described above.

  Table 14 shows the gas circulation time in each step. Table 18 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significant reduction in the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 9995 minutes.

Example 9
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added as a seed crystal to the aqueous solution to form a raw material composition, and ethanol produced as a by-product was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 25 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI type zeolite is 0.43 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopore The half width was 15 nm and μ = 17 nm. Moreover, the pore volume of the uniform mesopores was 0.40 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 93%. Table 13 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI-type zeolite was used as an aromatic compound production catalyst, n-butane was used as a raw material, and a conversion reaction to an aromatic compound was performed under the above-described conditions.

  Table 14 shows the gas circulation time in each step.

  Table 19 shows the raw material gas circulation time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significant reduction in the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 9995 minutes.

Example 10
Using the MFI-type zeolite obtained in Example 9 as an aromatic compound production catalyst, a conversion reaction to an aromatic compound using isobutene as a raw material was performed. The reaction was performed under the conditions described above.

  Table 14 shows the gas circulation time in each step. Table 20 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed continuously until the conversion time, benzene yield, toluene yield, and xylene yield were not significantly reduced until the feed gas circulation time of 9795 minutes.

Example 11
The MFI zeolite obtained in Example 9 was used as an aromatic compound production catalyst, and a conversion reaction to an aromatic compound was performed using n-hexane as a raw material. The reaction was performed under the conditions described above.

  Table 14 shows the gas circulation time in each step. Table 21 shows the raw material gas flow time, the conversion rate, and the yield of each product. Until the feed gas flow time of 10495 minutes, it was possible to obtain a product feed continuously without any significant decrease in conversion, benzene yield, toluene yield, or xylene yield.

Example 12
Using the MFI zeolite obtained in Example 9 as an aromatic compound production catalyst, a conversion reaction to an aromatic compound using methylcyclopentane as a raw material was performed. The reaction was performed under the conditions described above.

  Table 14 shows the gas circulation time in each step. Table 22 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed continuously until the conversion time, the benzene yield, the toluene yield, and the xylene yield were not significantly reduced until the raw material gas circulation time of 9995 minutes.

Comparative Example 7
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H ₂ O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was 180 ° C., to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of uniform mesopores in the pore distribution curve is 0.3 nm and μ = 4 nm. there were. Moreover, the pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. Table 13 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, n-butane was used as a raw material, and a conversion reaction was performed under the above-described conditions.

  Table 14 shows the gas circulation time in each step.

  Table 23 shows the raw material gas flow time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time of 9995 minutes, and it was difficult to say stable production.

Comparative Example 8
The conversion reaction was carried out under the above-mentioned conditions using the MFI zeolite obtained in Comparative Example 7 as a catalyst and isobutane as a raw material.

  Table 14 shows the gas circulation time in each step.

  Table 24 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 9795 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 9
The conversion reaction was performed under the above-described conditions using the MFI-type zeolite obtained in Comparative Example 7 as a catalyst and n-hexane as a raw material.

  Table 14 shows the gas circulation time in each step.

  Table 25 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 10495 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 10
Using the MFI zeolite obtained in Comparative Example 7 as a catalyst and methylcyclopentane as a raw material, the conversion reaction was carried out under the conditions described above.

  Table 14 shows the gas circulation time in each step.

  Table 26 shows the raw material gas circulation time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time of 9995 minutes, and it was difficult to say stable production.

Comparative Example 11
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 9 to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half-width of the peak of uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. . Further, the pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst and n-butane as a raw material, a conversion reaction was carried out under the above-described conditions.

  Table 14 shows the gas circulation time in each step.

  Table 27 shows the raw material gas flow time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say stable production.

Comparative Example 12
The conversion reaction was performed under the above-described conditions using the MFI-type zeolite obtained in Comparative Example 11 as a catalyst and isobutane as a raw material.

  Table 14 shows the gas circulation time in each step.

  Table 28 shows the raw material gas distribution time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 9795 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 13
The conversion reaction was performed under the above-described conditions using the MFI-type zeolite obtained in Comparative Example 11 as a catalyst and n-hexane as a raw material.

  Table 14 shows the gas circulation time in each step.

  Table 29 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Until the raw material gas circulation time of 10495 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 14
Using the MFI zeolite obtained in Comparative Example 11 as a catalyst and methylcyclopentane as a raw material, a conversion reaction was performed under the above-described conditions.

  Table 14 shows the gas circulation time in each step.

  Table 30 shows the raw material gas circulation time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say stable production.

Example 13
Amorphous aluminosilicate gel was added and suspended in an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The amount of seed crystals added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. By-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized with stirring at 115 ° C. for 4 days to obtain a slurry mixture. The slurry-like mixed liquid after crystallization was subjected to solid-liquid separation with a centrifugal settling machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

  10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI zeolite. Thereafter, the ammonium type MFI zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 28 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an agglomerated diameter of 46 μm. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.38 ml / g. Further, the mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. Moreover, the pore volume of uniform mesopores was 0.30 ml / g, and the ratio of the pore volume of uniform mesopores to the total pore volume of mesopores was 78%. Table 31 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  Using the obtained MFI-type zeolite as a catalyst, an aromatic compound was produced using a mixture of 50 mol% of 1-butene and 50 mol% of 2-butene as a raw material. The conditions on the reaction side and regeneration side of the swing reactor at that time were as follows.

(Reaction side)
The source gas was passed through the reaction tube heated at 600 ° C. for 500 minutes, and then the source gas feed was immediately switched to the direction of the reaction tube on the regeneration side.

(Playback side)
At the same time as the feed gas feed of the reaction side reaction tube is started, a nitrogen purge (1) is started on the regeneration side reaction tube heated at 600 ° C. Replaced. Next, the supply gas was immediately switched from nitrogen to air, and an air purge was performed for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, the catalyst was regenerated by circulating air for 60 minutes. Subsequently, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purge (3) was performed for 390 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, the nitrogen gas feed line was immediately switched in the direction of the reaction tube on the reaction side, and at the same time, the feed of the raw material gas was started in the reaction tube on the regeneration side. Thereafter, a series of processes similar to those described above were repeated to obtain a product feed continuously. The reactions described in the following examples and comparative examples were also operated in the same procedure, and only the raw material gas circulation time, the regeneration treatment time, and the nitrogen purge (3) time were changed. Table 32 shows the gas circulation time in each step.

  Table 33 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 4995 minutes.

Example 14
The MFI zeolite obtained in Example 13 was used as an aromatic compound production catalyst, and a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol%, isobutane 20 mol% was used as a raw material. A conversion reaction to an aromatic compound was performed under the conditions described above.

  Table 32 shows the gas circulation time in each step. Table 34 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Example 15
Using the MFI zeolite described in Example 13 as a catalyst, a conversion reaction was performed using a mixture of 29 mol% of 1-butene, 17 mol% of 2-butene, 47 mol% of isobutene, 5 mol% of n-butane, and 2 mol% of isobutane as raw materials. In addition, the raw material composition used in the present example assumes a mixture obtained by removing 1,3-butadiene from a C4 fraction obtained by ordinary naphtha decomposition.

  Table 32 shows the gas circulation time in each step. Table 35 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Example 16
Using the MFI zeolite described in Example 13 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 49 mol%, 2-butene 29 mol%, isobutene 10 mol%, n-butane 9 mol%, and isobutane 3 mol% as raw materials. In addition, the raw material composition used in the present example assumes a mixture obtained by removing a part of 1,3-butadiene and isobutene from a C4 fraction obtained by ordinary naphtha decomposition.

  Table 32 shows the gas circulation time in each step. Table 36 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Example 17
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added as a seed crystal to the aqueous solution to obtain a raw material composition. The generated ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
This raw material composition was reacted and treated in the same manner as in Example 13 to obtain an MFI type zeolite. The obtained MFI-type zeolite had an average particle size of 27 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.41 ml / g.

  The full width at half maximum of the peak of uniform mesopores in the pore distribution curve of the obtained MFI type zeolite was 15 nm, and the center value was 17 nm. Moreover, the pore volume of the uniform mesopores was 0.38 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 92%.

  Table 31 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was performed using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

  Table 2 shows the gas circulation time in each step. Table 37 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 4995 minutes.

Example 18
Using the MFI zeolite described in Example 17 as a catalyst, a conversion reaction was performed using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol%, and isobutane 20 mol% as raw materials.

  Table 32 shows the gas circulation time in each step. Table 38 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Example 19
Using the MFI zeolite described in Example 17 as a catalyst, a conversion reaction was carried out using a mixture of 29 mol% of 1-butene, 17 mol% of 2-butene, 47 mol% of isobutene, 5 mol% of n-butane, and 2 mol% of isobutane. In addition, the raw material composition used in the present example assumes a mixture obtained by removing 1,3-butadiene from a C4 fraction obtained by ordinary naphtha decomposition.

  Table 32 shows the gas circulation time in each step. Table 39 shows the feed gas circulation time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Example 20
Using the MFI zeolite described in Example 17 as a catalyst, a conversion reaction was carried out using a mixture of 49 mol% of 1-butene, 29 mol% of 2-butene, 10 mol% of isobutene, 9 mol% of n-butane and 3 mol% of isobutane as raw materials. In addition, the raw material composition used in the present example assumes a mixture obtained by removing a part of 1,3-butadiene and isobutene from a C4 fraction obtained by ordinary naphtha decomposition.

  Table 32 shows the gas circulation time in each step. Table 40 shows the raw material gas circulation time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 5995 minutes.

Comparative Example 15
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The generated ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H 2 O / Si molar ratio = 18
This raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was 180 ° C. to obtain an MFI type zeolite. The obtained MFI-type zeolite had an average particle size of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.05 ml / g.

  Further, the half width of the peak of uniform mesopores in the pore distribution curve of the obtained MFI type zeolite was 0.3 nm, and the center value was 4 nm. Moreover, the pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%.

  Table 31 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was performed using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

  Table 32 shows the gas circulation time in each step.

  Table 41 shows the raw material gas circulation time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time of 4995 minutes, and it was difficult to say stable production.

Comparative Example 16
Using the MFI zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol%, and isobutane 20 mol% as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 42 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 17
Using the MFI zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 29 mol% 1-butene, 17 mol% 2-butene, 47 mol% isobutene, 5 mol% n-butane, and 2 mol% isobutane as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 43 shows the feed gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 18
Using the MFI zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 49 mol%, 2-butene 29 mol%, isobutene 10 mol%, n-butane 9 mol%, and isobutane 3 mol% as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 44 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 19
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The generated ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
This raw material composition was reacted and treated in the same manner as in Example 13 to obtain an MFI type zeolite. The obtained MFI-type zeolite had an average particle size of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.20 ml / g.

  Further, the half width of the peak of uniform mesopores in the pore distribution curve of the obtained MFI type zeolite was 3 nm, and the center value was 6 nm. Further, the pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%.

  Table 31 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was performed using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

  Table 32 shows the gas circulation time in each step.

  Table 45 shows the feed gas flow time, the conversion rate, and the yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time of 4995 minutes, and it was difficult to say stable production.

Comparative Example 20
Using the MFI zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol% and isobutane 20 mol% as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 46 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 21
Using the MFI zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 29 mol% of 1-butene, 17 mol% of 2-butene, 47 mol% of isobutene, 5 mol% of n-butane, and 2 mol% of isobutane as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 47 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 22
Using the MFI zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 49 mol% 1-butene and 29 mol% 2-butene, 10 mol% isobutene, 9 mol% n-butane, and 3 mol% isobutane as raw materials.

  Table 32 shows the gas circulation time in each step.

  Table 48 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to the raw material gas circulation time of 5995 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Example 21
Amorphous aluminosilicate gel was added and suspended in an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. The amount of seed crystals added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. By-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized with stirring at 115 ° C. for 4 days to obtain a slurry mixture. The slurry-like mixed liquid after crystallization was subjected to solid-liquid separation with a centrifugal settling machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

  10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI zeolite. Thereafter, the ammonium type MFI zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an agglomerated diameter of 46 μm. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.39 ml / g. Further, the mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. Moreover, the pore volume of uniform mesopores was 0.31 ml / g, and the ratio of the pore volume of uniform mesopores to the total pore volume of mesopores was 79%. Table 49 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI-type zeolite was used as an aromatic compound production catalyst, and 1-hexene 50 mol% and 2-hexene 50 mol% were used as raw materials, and an aromatic compound was produced under the conditions described above. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The source gas was circulated for 430 minutes through the reaction tube heated at 600 ° C., and then the source gas feed was immediately switched in the direction of the reaction tube on the regeneration side.

(Playback side)
At the same time as the feed gas feed of the reaction side reaction tube is started, a nitrogen purge (1) is started on the regeneration side reaction tube heated at 600 ° C. Replaced. Next, the supply gas was immediately switched from nitrogen to air, and an air purge was performed for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, the aromatic compound production catalyst was regenerated by circulating air for 60 minutes. Subsequently, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purge (3) was performed for 320 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, the nitrogen gas feed line was immediately switched in the direction of the reaction tube on the reaction side, and at the same time, the feed of the raw material gas was started in the reaction tube on the regeneration side. Thereafter, a series of processes similar to those described above were repeated to obtain a product feed continuously. In the reactions described in the following examples and comparative examples, the operation was performed in the same procedure, and only the material gas circulation time and the nitrogen purge (3) time were changed. Table 50 shows the gas circulation time in each step.

  Table 51 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4295 minutes, it was possible to stably obtain a product feed without any significant decrease in conversion, benzene yield, toluene yield, and xylene yield.

Example 22
The MFI-type zeolite obtained in Example 21 was used as an aromatic compound production catalyst, and a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% was used as a raw material, and a conversion reaction to an aromatic compound was performed under the conditions described above. It was.

  Table 50 shows the gas circulation time in each step. Table 52 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without significantly reducing the conversion rate, benzene yield, toluene yield and xylene yield until the raw material gas circulation time of 4195 minutes.

Example 23
The MFI-type zeolite obtained in Example 21 was used as an aromatic compound production catalyst, and a mixture reaction of 50 mol% 1-hexene and 50 mol% n-hexane was used as a raw material, and a conversion reaction to an aromatic compound was performed under the above-described conditions. It was.

  Table 50 shows the gas circulation time in each step. Table 53 shows the raw material gas circulation time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without any significant decrease in the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 7295 minutes.

Example 24
The MFI-type zeolite obtained in Example 21 was used as an aromatic compound production catalyst, and a mixture of n-hexane 50 mol% and cyclohexane 50 mol% was used as a raw material, and a conversion reaction to an aromatic compound was performed under the conditions described above.

  Table 50 shows the gas circulation time in each step. Table 54 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed stably without any significant decrease in the conversion rate, benzene yield, toluene yield, and xylene yield until the raw material gas circulation time of 8895 minutes.

Example 25
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added as a seed crystal to the aqueous solution to form a raw material composition, and ethanol produced as a by-product was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 21 to obtain MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI type zeolite is 0.42 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopore The half width was 15 nm and μ = 17 nm. The pore volume of the uniform mesopores was 0.39 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 91%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Moreover, in the powder X-ray diffraction of the obtained MFI type zeolite, no peak exists in the range of 0.1 to 3 degrees, and it is shown that the mesopores are irregularly connected.

  The obtained MFI-type zeolite was used as an aromatic compound production catalyst, and a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% was used as a raw material, and a conversion reaction into an aromatic compound was performed under the above-described conditions.

  Table 50 shows the gas circulation time in each step.

  Table 55 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4295 minutes, it was possible to stably obtain a product feed without any significant decrease in conversion, benzene yield, toluene yield, and xylene yield.

Example 26
The MFI type zeolite obtained in Example 25 was used as an aromatic compound production catalyst, and a conversion reaction to an aromatic compound was performed using a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material. The reaction was performed under the conditions described above.

  Table 50 shows the gas circulation time in each step. Table 56 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed continuously until the conversion rate, the benzene yield, the toluene yield, and the xylene yield were not greatly reduced until the raw material gas circulation time of 4195 minutes.

Example 27
Using the MFI-type zeolite obtained in Example 25 as an aromatic compound production catalyst, a conversion reaction to an aromatic compound was performed using a mixture of 1-hexene 50 mol% and n-hexane 50 mol% as a raw material. The reaction was performed under the conditions described above.

  Table 50 shows the gas circulation time in each step. Table 57 shows the raw material gas flow time, the conversion rate, and the yield of each product. It was possible to obtain a product feed continuously until the conversion time, benzene yield, toluene yield, and xylene yield were not significantly reduced until the feed gas flow time of 7295 minutes.

Example 28
Using the MFI-type zeolite obtained in Example 25 as an aromatic compound production catalyst, a conversion reaction to an aromatic compound using n-hexane 50 mol% and cyclohexane 50 mol% as raw materials was performed. The reaction was performed under the conditions described above.

  Table 50 shows the gas circulation time in each step. Table 58 shows the raw material gas flow time, the conversion rate, and the yield of each product. Until the feed gas flow time of 8895 minutes, it was possible to obtain a product feed continuously without any significant decrease in conversion, benzene yield, toluene yield, or xylene yield.

Comparative Example 23
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H 2 O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 21 except that the crystallization temperature was changed to 180 ° C. to obtain MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of uniform mesopores in the pore distribution curve is 0.3 nm and μ = 4 nm. there were. Moreover, the pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. Table 49 shows the physical properties of the obtained MFI-type zeolite.

  Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was carried out under the above-described conditions using a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% as a raw material.

  Table 50 shows the gas circulation time in each step.

  Table 59 shows the raw material gas distribution time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 24
Using the MFI zeolite obtained in Comparative Example 23 as a catalyst, a conversion reaction was performed under the above-described conditions using a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material.

  Table 50 shows the gas circulation time in each step.

  Table 60 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4195 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 25
Using the MFI zeolite obtained in Comparative Example 23 as a catalyst, a mixture of 50 mol% 1-hexene and 50 mol% n-hexane was used as a raw material, and a conversion reaction was performed under the above-described conditions.

  Table 50 shows the gas circulation time in each step.

  Table 61 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 7295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 26
Using the MFI-type zeolite obtained in Comparative Example 23 as a catalyst, n-hexane 50 mol% and cyclohexane 50 mol% were used as raw materials, and a conversion reaction was performed under the above-described conditions.

  Table 50 shows the gas circulation time in each step.

  Table 62 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 8895 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 27
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as seed crystals to the resulting suspension to obtain a raw material composition. By-product ethanol was removed by evaporation.

  In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 21 to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half-width of the peak of uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. . Further, the pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. Table 49 shows the physical properties of the obtained MFI-type zeolite.

  The obtained MFI-type zeolite was used as a catalyst, and a conversion reaction was performed under the above-described conditions using a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% as a raw material.

  Table 50 shows the gas circulation time in each step.

  Table 63 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 28
Using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst, a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% was used as a raw material, and a conversion reaction was performed under the above-described conditions.

  Table 50 shows the gas circulation time in each step.

  Table 64 shows the raw material gas circulation time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 4195 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 29
Using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst, a conversion reaction was performed under the above-described conditions using a mixture of 1-hexene 50 mol% and n-hexane 50 mol% as a raw material.

  Table 50 shows the gas circulation time in each step.

  Table 65 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 7295 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

Comparative Example 30
Using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst, n-hexane 50 mol% and cyclohexane 50 mol% were used as raw materials, and a conversion reaction was performed under the above-described conditions.

  Table 50 shows the gas circulation time in each step.

  Table 66 shows the raw material gas flow time, the conversion rate, and the yield of each product. Up to a raw material gas circulation time of 8895 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say stable production.

  The catalyst for producing an aromatic compound of the present invention contains an MFI type zeolite characterized by mesopores, so that the aromatic compound can be produced from hydrocarbon raw materials such as lower olefins, saturated aliphatic hydrocarbons and alicyclic hydrocarbons. Is produced, it is possible to obtain a specific long catalyst life, to be excellent in productivity and to be a stable production method, and is very useful industrially.

Claims (13)

An aromatic compound production catalyst comprising an MFI-type zeolite that satisfies the following properties (i) to (iii):
(I) The mesopore distribution curve has a peak, the half width (hw) of the peak is hw ≦ 20 nm, and the central value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, which corresponds to the peak The mesopore volume (pv) of the mesopores is 0.05 ml / g ≦ pv.
(Ii) No powder has a peak in the range of 0.1 to 3 degrees in powder X-ray diffraction measurement with a diffraction angle of 2θ.
(Iii) The average particle size (PD) is PD ≦ 100 nm. 2. The aromatic compound production catalyst according to claim 1, comprising an MFI-type zeolite having a mesopore group in which the half width shown in (i) is hw ≦ 15 nm. It comprises a MFI-type zeolite having a mesopore group in which the ratio of the pore volume to the total mesopore volume of pv shown in (i) (pvr) is 30% ≦ pvr ≦ 100%, The aromatic compound production catalyst according to claim 1 or 2. SiO ₂ / _Al 2 _{O 3} (molar ratio) containing MFI zeolite of _{20 ≦ SiO 2 / Al 2 O} 3 ≦ 200, aromatics production according to claim 1, characterized in that catalyst. The aromatic compound production catalyst according to any one of claims 1 to 4, wherein the catalyst is for swing operation. The aromatic compound production catalyst according to any one of claims 1 to 5, which is used for conversion of an aromatic compound of a saturated aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 6 carbon atoms. A method for producing an aromatic compound, wherein the aromatic compound production catalyst according to claim 1 is contacted with a hydrocarbon having 2 to 6 carbon atoms to form an aromatic compound. The method for producing an aromatic compound according to claim 7, wherein the hydrocarbon having 2 to 6 carbon atoms is a lower olefin containing at least one selected from the group consisting of olefins having 2 to 6 carbon atoms. The method for producing an aromatic compound according to claim 7, wherein the hydrocarbon having 2 to 6 carbon atoms is a hydrocarbon mixture having 4 and / or 6 carbon atoms. The method for producing an aromatic compound according to claim 9, wherein the hydrocarbon mixture having 4 and / or 6 carbon atoms is a fraction produced by naphtha pyrolysis. The method for producing an aromatic compound according to claim 7, wherein the hydrocarbon having 2 to 6 carbon atoms is a saturated aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 6 carbon atoms. The method for producing an aromatic compound according to any one of claims 7 to 11, wherein the aromatic compound contains at least one of the group consisting of benzene, toluene and xylene.   A plurality of reaction fields having the aromatic compound production catalyst according to any one of claims 1 to 6, wherein at least one reaction field is an aromatic compound in a swing operation in which the aromatic compound production catalyst is regenerated. The method for producing an aromatic compound according to any one of claims 7 to 12.